Water-repellent process



- processing of the fabric.

Patented Sept. 30, 1941 WATER-BEPELLENT PROCESS Herman A. Bruson andLouis H. Bock, Philadelph-ia, Pa., assignors to Riihm & Haas Company,

Philadelphia, Pa.

No Drawing. Application December 29, 1938, Serial No. 248,196

7 Claims.

This invention relates to a new process of rendering textile fabrics,yarns, and fibers waterrepellent without materially altering the generalappearance of the fabric.

Water-repellency is obtained by imparting t the surface of fibers a waxyfinish which is not easily wet by water. In the usual process ofwaterproofing fabrics the surface of the fabric is coated with asuperficial layer of a wax or a metallic soap. These water-repellingsubstances are relatively easily removed by solvents in dry cleaningbaths or by hot soap solutions in laundering. Recently various chemicaltreatments. of cellulose fibers have been suggested, but thus far thesemethods have suffered from certain disadvantages, such as resulting lossof tensile strength or evolution of unpleasant or toxic fumes during theThe object of this invention is to provide a process of imparting tofibers, yarns, and fabrics a highly water-repellent finish which ispermanent to'laundering and dry cleaning. Another object is to impartthe property of water-repel lency to all the fibers within the fabricand avoid superficial coating of fabric. A further object is 'to providepermanent water-repellency with retention of the strength of the fabric.A further object is to provide water-repelling agents which do notevolve toxic fumes during processing.

It has been found that these objects may be attained by the use ofcompounds possessing the following general structure-' /A a -Grim inwhich Ar represents an aromatic nucleus of the bound oxygen may be partof a hydroxyl group or part of a side chain. In the above formula A andB represents members of the group consisting of open chain, loweraliphatic groups when taken singly and when taken together divalentgroups which jointly with the nitrogen form a heterocycla/ Thehydrocarbon substituents may be such groups as primary,'secondary, ortertiary octyl,

dodecyl, hexadecyl or octadecyl groups unsaturated groups such. asundecenyl or octadecenyl,

alicyclic groups such as bornyl, camphyl; naphthenyl or butylcyclohexyl. More than one such group may be present.

The compounds may be obtained by condensing a phenolic derivativecontaining an aliphatic or cycloaliphatic side chain of at least eightcarbon atoms with formaldehyde and a non-aromatic secondary amine. Inanother modification a suitable phenol is condensed with formaldehydeand a non-aromatic secondary amine and the hydroxyl group is esterifiedwith an acyl halide containing more thanseven carbon atoms or thehydroxyl group may be etherified with a long chain hydrocarbon group.

These compounds may be used in the form of the free base or in the formof a salt obtained by neutralizing the base with an organic or inorganicacid or by reacting with an agent for alkylation to yield a quaternaryammonium salt.

Compounds possessing the essential groups and linkages have beendescribed in U. S. patents to Bruson Nos. 2,033,092; 2,040,039 and2,040,040 and in U. S. Serial No. 240,009 filed November 12, 1938, nowPatent No. 2,218,739, andin U. S. Serial No. 244,923 filed December 1,1938.

The quaternary ammonium salts are usually the preferred form for usesince they may be used directly in aqueous baths with or without acatalyst. The catalyst may be acidic or basic as desired. But, as shownabove, either the base or the salt forms may be used by being taken upin water or other solvent for application to fabrics or yarns.Dispersions or solutions are quite stable.

Products of the general type described have the advantages of being welldispersed or dissolved by water and being soap-like in properties,providing wetting and penetrating actions. They are adsorbed by thefibers and when the fabric is subsequently heated, these compounds reactwith the fibers to form water-repellent derivatives of the fibersthemselves. The wetting and peneincludes the usual sort of solution andthe dispersions of the molecular aggregates.

While it may appear surprising at first glance that a soap-like compoundwhich possesses wetting, penetrating and emulsifying propertiessoap-like molecule.

should become agood water-repellent, the behavior is readily explained.All capillary-active compounds contain within their molecules polar andnon-polar groupings. Ordinarily, it is not easy to separate these twoparts of the molecule. The applicants have found, however, that certaincompounds which possess the aryl methylene nitrogen-linkage aredecomposed, when heated on fibers, with the formation of a compound ofaged by heating to 120 -C. or more may be treated by the hereindisclosed process.

The process of treating fabric, yarn, or even.

loose fiber is relatively simple. The material to be treated isimpregnated with the solution by any convenient method, such as padding,dipa ping, spraying, etc. Then, with or without. pre-.'

vious drying, the material is subjected to a tem-' perature high enoughto bring about thereaction of the compound and the fiber. The preferredtemperature for this reaction is above about 120 C. The time requiredfor the reaction will vary with the temperature used. At 120 C.,forexample, an hour may be required, whereas two or three minutes isusually sufficient at 150 C. It is desirable to remove the by-productsof the reaction by washing the textile material after it has beenheated.

Solutions containing the tertiary salts and also solutionscontaining thequaternary salts are usually acid. 'The excess acid seems to serve as acatalyst in promoting the reaction between the compound and 'the fibers,although a catalyst is not essential to the process. On the other hand,

it has been found that alkaline salts such as sodium carbonate or sodiumacetate are also useful catalysts in the reaction.

Not all the aryl-methylene nitrogen compounds are soluble in mildlyalkaline-solutions.-

Those compounds. however, containing a free hydroxyl group tend to besoluble.- Compounds derived from acyl phenols are usually suflicientlysoluble 'in slightly alkaline solutions to permit their use in this way.There is .practically no danger of tendering fabric with such solutions.

The'following examples are given to illustrate the method of renderingfibers water-repellent but they are not to be interpreted as limitationsthereof. g

- Example 1.-Cotton broadcloth was immersed inza solution containing 5parts of acetic acid, 8'7 parts of water and 8- parts of thecondensation product of equimolecular quantities of octadecyl phenol,formaldehyde and dimethylamine having the formula- The cloth was driedat room temperature and baked 30 minutes at 130 C. It .was verywaterparts of water and 5 parts of the condensation product of octadecylphenol, formaldehyde and morpholine having the formula- CllH87 l 3 HCHa-CH:

o CHz-Ci The fabric was squeezed as dry as possibleand pressed with ahotflat iron for 3 minutes. A wash-fast, water-repellent finish resulted.

Example 3.-Viscose rayon was treated with a solution containing 8 partsof hexadecyl-hydroxybenzyl-diethylamine (obtained by the condensation ofhexadecyl phenol with formaldehyde and diethylamine), 5 parts of formicacid, and 8'7 parts of water. The material was driedin an oven at 130 C.for one hour. Good waterrepellency was obtained.

Example .4.-Wool fabric was wet out in a solution containing 10 parts ofthe oleic acid estr of hydroxybenzyl dimethyl benzyl ammonium chloridein 90 parts of water. The fabric was dried at roomtemperature and bakedin a closed oven 30 minutes at 130 C. The finished material had'excellent water-repellency which resisted a hot soap wash.

. Example 5.Cotton sheeting was immersed in a solution containing 5parts of acetic acid, 87 parts of water and 8 parts of thefi-chloroethoxy ethyl ether of the condensation product of p-(a, a, y,v-tetramethylb'utyl) phenol, formaldehyde and dimethylamine. The'fabric'was placed in an oven at 150 C.-, for 10 minutes. After washing,the material retained a considerable degree of water-repellency.

Erample 6.Cotton yarn was immersed in a solution containing 10 parts ofthe lauric ester' of hydroxyl benzyl dimethyl benzyl ammonium chlorideand 90 parts of water. After drying-at a solution containing 10 parts ofthe condensation product of stearoyl phenol, formaldehyde ter-repellentafter washing in hot soap solution.

Example 9.Cotton sheeting was immersed in I a solution-containing 10parts of p-stearamidohydroxy benzyl-dimethylamine and 100 parts of watercontaining 5 g. of acetic acid. After drying at room temperature it washeated 10 minutes at 135 C. A good water-repellent finish was obtained.The stearamido hydroxybenzyl dimethylamine was obtained by heatingequimolecular 'quantit'es of 'p-stearamidophenol, formaldehyde and,dimethylamine in alcohol solution for 2 hours.

While agents of the sort described herein may I be applied in organicsolvents, treatment of fab repellent and it retained this property afterrepeated washing in hot soap solution.

Erample 2.Cotton sheeting was immersed in a ,solution containing 5 partsof acetic acid, 90

ric with the agents in water avoids the hazards apt to be inflammable ortoxic. tion the use of soap-like materials not only provides wetting andpenetrating actions but also emulsifying action, which-permits theincorpora tion of small amounts of waxes or other inexpensivewaterproofing agents in the treating bath. While such waxes are notpermanent, like the reaction product of the aryl-methylene amines withfibers, they aid initial repellency at a minimum of expense. Whether thenew water-repellent agents are used alone or in combination with otherwater-repellent materials, they oiier the advantage of a one-bathprocess.

We claim:

1. The process of treating textile material, which comprisesimpregnating the material with a compound selected from the groupconsisting of phenolic-methylene tertiary amines in which two of theN-substituents are chosen from the group consisting of open chain, loweraliphatic groups and divalent groups which jointly with the nitrogenform a heterocyclic ring and in which the phenolic group bears anorganic subsubsequently heating said textile material to react thebenzyl dimethylamine therewith.

4. The process of treating textile material, which comprisesimpregnating the material with an aqueous solution of an acid salt of abenzyl amine in which two of the N-substituents are lower aliphaticgroups and in which the phenyl which comprises impregnating the materialwith a bath containing a benzyl amine in which two of the N-substituentsare lower aliphatic groups amine therewith.

3. The process of treating textile material,

- which comprises impregnating the textile material with an alkalineaqueous dispersion of octadecyl hydroxy benzyl dimethylamine, and

group carries nuclearly-bound oxygen atom and a hydrocarbon substituentof at least eight carbon atoms obtainable from the aliphatic andallcyclic series, and subsequently heating said textile material toreact the benzyl amine therewith.

5. The process of treating textile material, which comprisesimpregnating the textile material with an aqueous solution of the aceticacid salt of octadecyi hydrox'y benzyl dimethylamine, and subsequentlyheating said textile material to react the benzyl dimethylaminetherewith.

6. The-process of treating textile material, which comprisesimpregnating the material with an aqueous solution of a quaternary saltof a benzyl' amine in which at least two of the N- substituents arelower aliphatic groups and in which the phenyl group contains asubstituent of at least eight carbon atoms obtainable from the aliphaticand alicyclic series Joined to the phenyl group by a carboxyl linkage,and subsequently heating said textile material to react the benzyl aminetherewith.

7. The process oftreating textile material, which comprises impregnatingthe material with an. aqueous solution of the oleic acid ester ofhydroxyl benzyl dimethyl benz'yl ammonium chloride, and subsequentlyheating said textile

